(1-alkylamino-2-anthraquinonylcar-bonylamido) alkyl trialkyl ammonium salts as disperse dyes for acrylic fibers



United Sta s ten 3C mes... Ffiifaifi I have found that certain cationicanthraquinone dyes I v 2,924,609 of the formula: (1 ALKYLAMINO 2ANTHRAQUINDNYLCAR- 0 NH-R" BONYLAMIDO)ALKYL TRIALKYL AMMONIUM SALTS ASDISPERSE DYES FOR ACRYLIC OONH(CHi)nNR A FIBERS y 1 AsaWillard Joyce,Plainfield, NJ. No Drawing. Original application September 25, 1957, ii

Serial No. 686,016. Divided and this application June 0 a 10, 1958,serial 741,006 in which R is the lower alkyl groupyR 1s lower alkyl,aralkyl or hydroxy lower alkyl and R" 18 lower alkyl or cyclo- 4 Claims.(Cl. 260-377) hexyl, n being an integer from 2 to 4 and A- being an g vp anion, are highly soluble dyes with excellent afiinity for Thisinvention relates to new cationic anthraquinone Polyacrylonitrile fibersof high acl'ylonitrile contentdisperse dyes for coloring acrylic fibers.More particular- The new cationic anthraquinone dyes of my invention ly,it relates to l-substituted amino anthraquinone-Z-carmay be readilyprepared from l-nitroanthraquindne-Z- boxamides having no other ringsubstituents, in which the Carbonyl chloride y reaction With Variousalkylene substituting group in the aid lubstituted amino, when aminesfollowed by replacement of the readily removable notlower alkyl, iscyclohexyl, and in which the said car- 20 nitro group by reaction withan alkylamine and finally boxamide group is a substituted carboxamide,the said quaternization of the resultant product to form thedyesubstituting'group beinga quaternary ammonium alkylene stuff. Thepreparation can be shown by the'following group, the quaternary ammoniumnitrogen of which is equation:

0 N 0: ll R II R l R"NH| COCl HgN-(CHaM-N-R CONH(CHa)-N\ I t .0 I i 0NH-R" '0 NHR P l R I R v R'A CO--NE (CHz),N\ CONH-(CH2)1YI\ A R R! Rsubstituted by three groups, at least two of which are lower Suitablediamines which may be reacted with the acid alkyl, the other being, whennot lower alkyl, a substituted chloride are compounds such asdimethylaminoethylalkyl which, when not aralkyl, is hydroxy lower alkyl.amine, diethylaminoethylamine, dimethylaminopropyl- This application isa division of my copending appliamine, diethylaminopropylamine,dimethylaminobutylcation Serial No. 686,016, filed September 25, 1957,amine, diethylaminobutylamine, and the like. Higher alnow abandoned. kylgroups can be placed on theamino group, such-as The polyacrylonitrilefibers, which have become 'inpropyl, butyl, and hexyl. Similarly, thealkyl groups creasingly useful articles of commerce, are difiicult toneed not be the same, so that one can use methylethyldye. Most of thecommercially available fibers of this aminoethylamine ormethylethylarninopropylarnine and type contain a major proportion ofpolyacrylonitrile. In the like. most cases over 85% of the fibers isacrylonitrile. Few of For the replacement of the nitro group any primarythe standard dyestuffs available show affinity for these alkylamine upto 6 carbon atoms can be used suchas high acrylonitrile content fibers.Especially it has been methylarnine, ethylamine, propylamine,isopropylamine, hard to obtain deep shades on these fibers, since deepbutylamine, isobutylamine, and the like and cyclohexylshades require astrong aifinity of the fiber for the dyeamine.

stuff. The only way to achieve deep shades has been to In thequaternization of the side chain amino group one increase the time andtemperature of the dyeing process. can use any quaternizing agent R'A inwhich R is the Such drastic conditions of dyeing result in injury to thequaternizing group and A is the anion which may contain fabrics. Theresistant properties of these fibers are dean organic residue. Examplesof quaternizing agents sirable for general textile use because theyrender the which may be used include dialkyl sulfates, such as difiberphysically durable. However, the problem of dyeing methyl sulfate,diethyl sulfate, dipropyl sulfate or dihas'been so great that thesedurable types which'are less butyl sulfate, alkyl halides such as methyliodide, ethyl durable physically unless methods of dyeing them readilyiodide, methyl chloride or ethyl chloride, propyl bromide, are found.The usual disperse dyes have little or no butyl bromide, hexyl bromideand the like, aralkyl halides afiim'ty for polyacrylonitrile fibers.Those basic dyes such as benzyl chloride, phenylethyl bromide, and thelike; which do dye fibers of this type give dyeings of poor alkyl estersof aryl sulfonic acids such as the methyl, fastness to light, also',suchadyes need dispersing agents ethyl, propyl or butyl esters oftoluene sulfonic acids or as solubilizing agents to disperse themproperly in the dye substituted alkyl halides such as ethylenechlorohydrin, bath, propylene chlorohydrin, and the like.

'3 The polyacrylonitriles which may be dyed by the-compounds of myinvention and which when dyed fall within the scope of my invention arethose polymers and copolymers of acrylonitrile which contain a majorproportion by weight of acrylonitrile. They may also contain basiccomonomers such as methyl vinyl pyridine and vinyl pyridine orcomonorners such as methyl acrylate, vinyl acetate and vinyl chloride.Of the polyacrylonitriles available commercially which can be used toform the polyacrylonitriles of my invention, one is 100%polyacrylonitrile, another is approximately 95% acrylonitrile andapproximately methyl acrylate, another has 89% of acrylonitrile, 6%methyl vinyl pyridine and 5% vinyl acetate and still another has acomposition of 94% acrylonitrile, 5% methyl vinyl pyridine and 1% vinylacetate. Polymers having as little as 50% acrylonitrile can be dyedby'this class of dyes of my invention to form the colored polymers of myinvention.

It is an advantage of my invention that the dyes may be dyed at the boilby the usual dispersed dyeing methods. It is a further advantage of myinvention that they are attractive bluish-red'shades of good fastness tolight. For example, a dyestufr of the formula:

CH3 OH;

mers in neutral to weakly alkaline dye bathsat the boil.

It is a further advantage of my invention that the cationic dyes claimedin this application also dye acetate, nylon and silk, as well as Vicaraand wool.

My invention can be illustrated by the followingexamples in which partsare by weight unless otherwise specified. The examples are intended toillustrate the invention and not to limit it.

Example 1 0 NEE-0:115 H CH;

o O-NHCH CHiCH -I I cans of CH; OH;

To 75 parts by volume of benzene at 25 C. is added 9.5 parts of1-nitroanthraquinone-2-carbonyl chloride. Then, gradually 6.3 parts ofdimethylaminopropylamine is added at 15-20" C. The mixture is stirred at15-20 C. until the reaction is complete (which takes about an hour andfifteen minutes when parts are grams). The product is isolated byfiltration, wished with benzene and dried. It is then slurried in 75parts of Water and sodium carbonate is added until the mixture isalkaline to phenolphthalein indicator paper. After further stirring, theproduct is again filtered, washed alkaline-free with water anddried.

To 60 parts by volume of toluene is added 5.7 parts of the above productand 2.7 parts by volume of 70% ethylarnine. The mixture is stirredseveral hours at -8590 C. and then at reflux (90-95 C.) until thereaction is complete. The resultant product l-ethylamino- 2 (Ndimethylaminopropylcarbamoyl)-anthraquinone is then isolated byevaporation of the mixture to dryness.

To 100 parts by volume of benzene is added 5.5 parts of the aboveethylamino ar thraquinone derivative and 1.5 parts by volume of dimethylsulfate. The mixture is warmed on a steam bath until quaternization iscomplete. It is then allowed to -cool and the quaternized product isfiltered, washed with benzene and dried at about C.

, Example? 0 Nn-omomorrr-om ll C2115 ,cofinni-omomonionr-fi BF fCgHi Lethyl ammonium dyes are obtained.

Example 3 CHr-Cgl 0 NH-CH CH1 H CHa-CH: /CH:

4- CONH-CH:CHrN-CH; 1"

If in Example 1, dimethylaminopropylarnine is replaced with anequivalent amount of dimethylammoethylamme,

the resultant nitro compound is then reacted with an equivalent amountof cyclohexylamine instead of ethylarnine, and the resultant'dye' isquaterni'zed with an excess of methyl iodide, a. cationic anthraquinonedye of the above formula is obtained which'dyes acrylic fibersbluish-red shades.

I claim: 1. Cationic anthraquinone dyes of the'fcrmula 0 Nut-R" H r R CO-NH(CH:) ,.N A

I IV R No refetencescited.

1. CATIONIC ANTHRAQUINONE DYES OF THE FORMULA